|Publication number||US4354958 A|
|Application number||US 06/202,578|
|Publication date||Oct 19, 1982|
|Filing date||Oct 31, 1980|
|Priority date||Oct 31, 1980|
|Publication number||06202578, 202578, US 4354958 A, US 4354958A, US-A-4354958, US4354958 A, US4354958A|
|Original Assignee||Diamond Shamrock Corporation|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (9), Non-Patent Citations (2), Referenced by (107), Classifications (15), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
In the field of electrochemistry there is a well known electrochemical cell known as a chlor-alkali cell. In this cell, an electric current is passed through a saturated brine (sodium chloride salt) solution to produce chlorine gas and caustic soda (sodium hydroxide). A large portion of the chlorine and caustic soda for the chemical and plastics industries are produced in chlor-alkali cells.
Such cells are divided by a separator into anode and cathode compartments. The separator characteristically can be a substantially hydraulically impermeable membrane, e.g., a hydraulically imperable cation exchange membrane such as the commercially available NAFIONŽ manufactured by the E. I. du Pont de Nemours & Company. Alternatively, the separator can be a porous diaphragm, e.g., asbestos which can be in the form of vacuum deposited fibers or asbestos paper sheet as are well known in the art. The anode can be a valve metal, e.g., titanium, provided with a precious metal coating to yield what is known in the art as a dimensionally stable anode.
One of the unwanted byproducts present in a chloralkali cell is hydrogen which forms at the cell cathode. This hydrogen increases the power requirement for the overall electrochemical process and eliminating its formation is one of the desired results in chlor-alkali cell operation.
It has been estimated that 25% of the electrical energy required to operate a chlor-alkali cell is utilized due to the formation of hydrogen at the cathode. Hence, the prevention of hydrogen formation at the cathode during the formation of hydroxide, can lead to substantial savings in the cost of electricity required to operate the cell. In fairly recent attempts to achieve cost savings and energy savings in respect of operating chlor-alkai cells, attention has been directed to various forms of what are known as oxygen (air) cathodes. These cathodes prevent the formation of molecular hydrogen at the cathode and instead reduce oxygen to form hydroxyl ions. Savings in cost for electrical energy are thereby achieved.
One known form of oxygen (air) cathode involves use of an active layer containing porous active carbon particles whose activity in promoting the formation of hydroxide may or may not be catalyzed (enhanced) using precious metal catalysts, such as silver, platinum, etc. The active carbon particles may become flooded with the caustic soda thereby significantly reducing their ability to catalyze the reduction of oxygen at the air cathode, resulting in decreased operating efficiency. In an attempt to overcome these difficulties in flooding of the active carbon, hydrophobic materials, e.g., polytetrafluoroethylene (PTFE) have been employed in particulate or fibrillated (greatly attenuated and elongated) form to impart hydrophobicity to the active carbon layer, per se, and/or to a protective (wet proofing) or backing sheet which can be laminated or otherwise attached to the active layer. Thus PTFE has been employed in both active layers and in backing (wetproofing) layers secured thereto. Such active carbon-containing layers, however, are subjected to loss of strength resulting in failure combined with blistering thereof when the chlor-alkali cell is operated at high current densities, viz., current densities ranging from about 250 milliamperes/cm2 and higher for prolonged time periods.
The present invention is particularly directed to an improved fibrillated matrix air electrode and a process for forming it such that the resulting coherent, self-sustaining sheet can be subsequently employed as the active layer when laminated to a backing sheet and current collector to form an oxygen (air) cathode having high durability and resistance to degradation due to the corrosive environment present in a chlor-alkali cell, fuel cell, etc. In other words, the fibrillated, matrix active layer produced in accordance with this invention is capable of long life with a lower rate of decline in operating voltage. The term matrix is employed herein in as much as it is believed that in an electrode of this type the catalyzed active carbon is thoroughly involved with assisting the reduction of oxygen within the cathode active layer while the carbon black and the PTFE act in one or more ways; (a) as a hydrophobic gas path, (b) as a conductive agent, which lowers the electrical resistance of the mixture from about 2 to 3 times, resulting in a better current distribution to the current collector, and (c) as a hydrophobic binder, incorporating the wet active carbon in a matrix of Teflon carbon black. Of course, however, the present invention is not dependent upon this or any theory for the operation thereof.
U.S. Pat. No. 3,838,064 to John W. Vogt et al is directed to a process for dust control involving mixing a finely divided fibrillatable polytetrafluoroethylene with a material which characteristically forms a dust to form a dry mixture followed by sufficient working to essentially avoid dusting. Very small concentrations of PTFE, e.g., from about 0.02 to about 3% by weight are applied to achieve the dust control. Corresponding U.S. Pat. No. 3,838,092 also to Vogt et al is directed to dustless compositions containing fibrous polytetrafluoroethylene in concentrations of about 0.02% to less than 1%, e.g., about 0.75% by weight of PTFE based on total solids. The active layers of this invention are readily distinguishable from both the John W. Vogt et al. patents (U.S. Pat. Nos. 3,838,064 and 3,838,092) which employ much lower concentrations of PTFE and for different purposes.
Additionally, British Pat. No. 1,222,172 discloses use of an embedded conductive metal mesh or screen (35) within a formed electrode (30) containing a particulate matrix (34) of polytetrafluoroethylene polymer particles (21) in which there are located dispersed electrically conductive catalyst particles (24) which can be silver-coated nickel and silver-coated carbon particles, viz., two different types of silver-coated particles in the PTFE particulate matrix, in an attempt to overcome an increase in resistance as silver is consumed in the gas diffusion fuel cells to which said British patent is directed.
U.S. Pat. No. 4,058,482 discloses a sheet material principally comprised of a polymer such as PTFE and a pore-forming material wherein the sheet is formed of co-agglomerates of the polymer and the pore former. This patent teaches mixing polymer particles with positively charged particles of a pore former, e.g., zinc oxide, to form co-agglomerates thereof followed by mixing same with a catalyst suspension so as to form co-agglomerates of catalyst and polyerm-pore- former agglomerates followed by pressing, drying, and sintering these co-agglomerates. Subsequent to this sintering, the pore former can be leached out of the electrodes.
U.S. Pat. No. 4,150,076 (a division of U.S. Pat. No. 4,058,482) is directed to the process for forming the sheet of U.S. Pat. No. 4,058,482, said process involving formation of polymer-pore-former co-agglomerates, distributing same as a layer on a suitable electrode support plate, for example a carbon paper, to form a fuel cell electrode by a process which includes pressing, drying, sintering, and leaching.
U.S. Pat. No. 4,170,540 to Lazarz et al discloses microporous membrane material suitable for electrolytic cell utilization, e.g., as a chlor-alkali cell separator, and formed by blending particulate polytetrafluoroethylene, a dry pore-forming particulate material, and an organic lubricant. These three materials are milled and formed into a sheet which is rolled to the desired thickness, sintered, and subjected to leaching of the pore-forming material. According to the present invention, when forming the sheet by passing the fibrillated mixture of PTFE carbon black with active carbon and with or without a fugitive particulate pore-forming agent through the rollers, special care is taken to avoid conditions which would cause the PTFE to sinter. The present invention is clearly distinguishable from U.S. Pat. No. 4,170,540, which contains no active carbon and does not function as a catalytic or active layer in an electrode.
British Pat. No. 1,284,054 is directed to forming an air- breathing electrode containing an electrolyte within an air-depolarized cell. This air-breathing electrode is made by hot pressing a fluoropolymer sheet containing a pore-forming agent on to a catalyst composition (containing silver) and a metallic grid member. According to page 3 of said British patent, the PTFE-pore-forming agent-paraffin wax containing sheet, is subjected to a solvent wash to remove the paraffin wax (lubricant and binder) and then sintered in a sintering furnace at the appropriate temperatures for sintering the fluorocarbon polymer. After the PTFE-containing sheet is sintered and while it still contains the pore-forming particles, it is then ready for application to the catalyst composition of the air electrode for the hot pressing operation. Hot pressing involves the use of pressures ranging from about 5,000 to about 30,000 psi in conjunction with temperatures ranging from about 200° F. to 400° F. The process of the present invention is readily distinguishable from British Pat. No. 1,284,054 in that the present invention avoids the use of wax, avoids the trouble and expense of removing the wax and does not use sintering thereby imparting greater porosity to the PTFE in fibrillated form in the finished electrode. Additionally, the present invention avoids the repeated stripping-folding over-rolling again procedures required in all the examples of British Pat. No. 1,284,054.
U.S. Pat. No. 3,385,780 to I-Ming Feng discloses a thin, porous electrode consisting of a thin layer of a polytetrafluoroethylene pressed against a thin layer of polytetrafluoroethylene containing finely divided platinized carbon, the platinum being present in amounts of 1.2 to 0.1 mg/cm2 in the electrically conductive face of the thin electrode, viz., the side containing the platinized carbon, viz., the active layer. A thermally decomposable filler material can be used, or the filler can be a material capable of being leached out by either a strong base or an acid. U.S. Pat. No. 3,385,780 also mentions a single unit electrode involving finely divided carbon in mixture with PTFE.
An article entitled "ON THE EFFECT ON VARIOUS ACTIVE CARBON CATALYSTS ON THE BEHAVIOR OF CARBON GAS-DIFFUSION AIR ELECTRODES":
1. "Alkaline Solutions " by I. Iliev et al appearing in the Journal of Power Sources, 1 (1976/1977) 35,46 Elsevier Sequoia S.A., Lausanne--printed in The Netherlands, at pages 35 to 46 of said Journal is directed to double-layer, fixed-zone Teflon-bonded carbon electrodes having a gas supplying layer of carbon black "XC-35" (not further defined by the author) wetproofed with 35% Teflon and an active layer consisting of a 30 mg/cm2 mixture of the same wetproofed material "XC-35" and active carbon (weight ratio of 1:2.5). These electrodes were sintered at 350° C. under pressure of 200 kg/cm2 and employed as oxygen (air) cathodes in alkaline test environments.
The present invention is readily distinguishable from the oxygen (air) cathodes of Iliev et al in that according to this invention, a strong unsintered active layer is obtained by a procedure whereby two components are separately formed, mixed, chopped, fibrillated and formed to a coherent, self-sustaining active layer sheet wherein the active carbon particles are present within an unsintered network of fibrillated carbon black-PTFE. Such sheets, after pressing to consolidate the material, have a tensile strength characteristically exceeding 100 psi and yield a matrix electrode having an unusual combination of high tensile strength with resistance to blistering under high current densities in use. It will be observed the conditions employed in formation of the two separately formed mixtures and fibrillation are insufficient to effect sintering of the PTFE contained in said matrix electrode. The Iliev et al electrodes made according to the description set forth in the experimental disclosure of Iliev et al obtain their strength by sintering under pressure, which this invention avoids, because sintering under pressure would adversely affect the porosity of the PTFE backing layer when laminated to an active layer and a current distributor to form an electrode. The active layer of this invention is suitably strengthened by fibrillation of the PTFE carbon mix and subsequently by pressing during electrode lamination.
The publication "Advances in Chemistry Series," copywright 1969, Robert F. Gould, (Editor), American Chemical Society Publications, contains at pages 13 to 23 an article entitled "A Novel Air Electrode" by H. P. Landi et al. The electrode described contains 2 to 8 percent PTFE, is produced without sintering and is composed of graphitic carbon (ACCO Graphite) or metallized graphitic carbon particles blended with a PTFE latex and a thermoplastic molding compound to form an interconnected net work which enmeshes the filter particles. This blend is molded into a flat sheet and the thermoplastic is then extracted. The present process employs non-graphitic active carbons, significantly higher concentrations of PTFE in the active layer while avoiding the use of thermoplastic molding compound and avoiding the necessity to remove same. Also, the active layer of this invention is formed by rolling a prefibrillated granular mix and no molding step is necessary. No indication is given by Landi et al as to the stability and/or durability of their air electrode and no life testing or data is include in said article. British Pat. No. 1,222,172 discloses use of an embedded conductive metal mesh or screen (35) within a formed electrode (30) containing a particulate matrix (34) of polytetrafluoroethylene polymer particles (21) in which there are located dispersed electrically conductive catalyst particles (24) which can be silver-coated nickel and silver-coated carbon particles, viz., two different types of silver-coated particles in the PTFE particulate matrix in an attempt to overcome an increase in resistance as silver is consumed in the gas diffusion fuel cells to which said British patent is directed.
This invention is directed to an electrode active layer comprising active carbon particles present within an unsintered network (matrix) of fibrillated carbon black-polytetrafluorethylene. The active carbon particles preferably contain silver or platinum and range in size from about 1 to 30 microns. The unsintered network (matrix) contains from about 25 to 35 weight parts of polytetrafluoroethylene and about 75 to 65 weight parts of carbon black having a surface area ranging from about 25 to 300 m2 per gram and particle sizes ranging from about 50 to 3000 angstroms. The active layer contains a pore-forming agent and the concentration of active carbon therein ranges from about 40 to 80 weight percent.
One stream (mixture), the matrixing mix component, is obtained by adding a dilute dispersion containing polytetrafluoroethylene (PTFE) e.g., duPont "Teflon 30" having a particle size of about from 0.05 to 0.5 microns in water to a mix of a carbon black, e.g., an acetylene black, and water in a weight ratio of from about 25 to 35 weight parts of PTFE to from about 65 to about 75 weight parts of carbon black to "Teflonate" the carbon black, viz., form an intimate mix of PTFE/carbon black particles; drying the aforementioned mixture and heat treating it to remove the PTFE wetting agent thereby resulting in a first component mix.
The second component, the active carbon-containing catalyst component, is comprised of an optionally catalyzed, preferably previously deashed and optionally particle size classified active carbon, having a particle size ranging from about 1 to about 30 microns and more usually from about 10 to about 20 microns.
Deashing can be done by pretreatment with caustic and acid to remove a substantial amount of ash from the active carbon prior to catalyzing same. The term ash refers to oxides principally comprised of silica, alumina, and iron oxides. The deashing of active carbon constitutes the subject matter of co-pending U.S. Patent application entitled "Active Carbon Conditioning Process," Ser. No. 202,580, filed on even date herewith in the name of Frank Solomon as inventor. The disclosure of this application is incorporated herein by reference. The thus deashed, classified, active carbon particles can then be catalyzed with a precious metal, e.g. by contacting with a silver or platinum precursor followed by chemical reduction with or without heat to deposit silver, platinum or other respective precious metal on the active carbon. The catalyzed carbon can be filtered, dried at temperatures ranging from about 80° C. to 150° C., with or without vacuum, to produce a second (active carbon catalyst) component or mixture.
These mixtures are then chopped together, with or without the addition of a particulate, subsequently removable (fugitive) pore-forming agent and then shear blended (fibrillated) at temperatures ranging from about 40° to about 60° C. for 2 to 10 minutes, e.g. 4 to 6 minutes in the presence of a processing aid or lubricant, e.g., a 50:50 mixture (by weight) of isopropyl alcohol and water, viz., when no pore former is used as bulking agent. When a water-soluble pore former is used, the lubricant can be isopropyl alcohol. The previously chopped mixture can be fibrillated using a mixer having a Sigma or similar blade. During this fibrillation step, the chopped mixture of the two-component mixes is subjected to shear blending forces, viz., a combination of compression and attenuation which has the effect of substantially lengthening the PTFE in the presence of the remaining components. This fibrillation is believed to substantially increase the strength of the resulting sheets formed from the fibrillated mixed components. After such fibrillating, the mixture is noted to be fibrous and hence, the term "fiberizing" is used herein as synonymous with fibrillating.
Subsequent to fibrillation, the mixture is dried, chopped for from one to ten seconds into a fine powder and formed into a sheet by rolling at 50° to 100° C. or by deposition on a filter. A pore-former, if one is employed as a bulking agent, can be then removed prior to electrode fabrication. In the event no pore former is employed, the matrix active layer sheet can be used (as is) as the active catalyst-containing layer of an oxygen (air) cathode, e.g., for use in a chlor-alkali cell, fuel cell, etc.
The present invention is based upon the discovery that the aforementioned blistering and structural strength problems encountered at high current densities in active layers of gas electrodes can be substantially overcome by a process involving: forming two separate components, one a matrixing mix component containing carbon black with polytetrafluoroethylene particles and heating treating this PTFE-carbon black mix at given temperature conditions; separately forming an active carbon-containing/catalyst component; combining these two separate components into a mix; chopping the mix and shear-blending the chopped mix (fibrillating same) in order to arrive at a readily formable matrix which can be formed, e.g., pressed between rolls, or deposited upon a filter paper as a forming medium, pressed and then used as the active layer in an oxygen (air) cathode. The present invention results in active layers having reduced carbon corrosion, higher conductivity and air-transport combined with strength when compared with prior structures. This results in electrodes which can be used longer and are more stable in use.
Tensile strength tests of the coherent, self-sustaining active layer sheets rolled from the fiberized material characteristically displayed approximately 50% greater tensile strength than unfiberized sheets. Life testing of electrodes employing the fibrillated (fiberized) active layer sheets of this invention resulted in approximately 8900 hours life at 300 milliamps/cm2 in 30% hot (60° to 80° C.) aqueous sodium hydroxide before failure. In addition to the advantages of longevity and strength, this process is easy to employ in making large batches of active layer by continuous rolling of the fibrillated mix resulting in a material uniform in thickness and composition. Furthermore, the process is easy to administer and control.
In accordance with one preferred embodiment of this invention, a water soluble pore-forming agent, e.g., sodium carbonate, is employed in the mixing step wherein the polytetrafluoroethylene dispersion is mixed with carbon black. Alternatively, the pore-forming agent can be added later, when the carbon black-PTFE mix and the catalyzed active carbon particles are mixed together and chopped.
In forming an initial mixture of carbon black and polytetrafluoroethylene, the usual particle size of the carbon black ranges from about 50 to about 3000 angstroms and it has a surface area ranging from about 25 to about 300 m2 /gram. The PTFE is preferably employed in aqueous dispersion form and the mixture of carbon black and polytetrafluoroethylene can contain from about 65 to about 75 weight parts of carbon black and about 35 to about 25 weight parts of PTFE. After mixing, the carbon black and PTFE are dried and then the dried initial mix is heated in air at temperatures ranging from about 250° to 325° C., and more preferably 275° to 300° C., for time periods ranging from 10 minutes to 1.5 hours and more preferably from 20 minutes to 60 minutes. This heating removes the bulk of the PTFE wetting agent.
The other component of the matrix electrode, viz., the active carbon, preferably "RB" carbon manufactured by Calgon, a division of Merck, is deashed as per Docket 3194 by contact with an aqueous alkali, e.g., sodium hydroxide, or equivalent alkali, and more usually aqueous sodium hydroxide having a sodium hydroxide concentration of about 28 to about 55 wt. % for 0.5 to 24 hours. After washing, the active carbon is then contacted with an acid, which can be hydrochloric acid, phosphoric acid, sulfuric acid, hydrobromic acid, etc., at ambient temperatures using aqueous acid solution having from about 10 to about 30 wt. % acid, based on total solution for comparable time periods. Subsequent to the contact with acid, the deashed active carbon particles are preferably catalyzed. The deashed particles are preferably catalyzed as by contact with a precursor of a precious metal catalyst. In the event that the silver is desired to be deposited within the pores of the active carbon, it is preferred to use silver nitrate as the catalyst precursor followed by removal of excess silver and chemical reduction with alkaline formaldehyde. This can be done as described and claimed in U.S. patent application Ser. No. 202,579 entitled "Process for Catalyst Preparation" filed of even date herewith in the name of Frank Solomon. The disclosure of this application is incorporated herein by reference.
On the other hand, in the event that it is desired to deposit platinum within the pores of the active carbon material, chloroplatinic acid can be used as a precursor followed by removal of excess chloroplatinic acid and chemical reduction using sodium borohydride or formaldehyde as a reducing agent. According to a preferred embodiment, the platinum is derived from H3 Pt(SO3)2 OH by the procedure set forth in U.S. Pat. No. 4,044,193. The reduction can be accompanied with the use of heat or it can be done at ambient room temperatures. After catalysis, the active carbon particles are filtered and vacuum dried as the active carbon-containing catalyst component in preparation for combination with the acetylene black PTFE matrixing component mix.
The carbon black/PTFE matrixing component mix preferably in a weight ratio ranging from about 65 to 75 weight parts of carbon black to 25 to 35 weight parts of PTFE, is mixed with the catalyzed deashed active carbon-containing component and subjected to chopping to blend the carbon black PTFE matrixing component with the catalyst component in the manner set forth above. This mix is then subjected to fibrillation (shear blending or fiberizing), for example in a mixer with appropriate blades at approximately 50° C. This shear blended material has a combination of good conductivity and high tensile strength with low Teflon content resulting in extraordinarily long life in use at high current densities in the corrosive alkaline environment present in a chlor-alkali cell.
The active layers of this invention can contain (after removal of any pore forming bulking agent therefrom) from about 40 to 80 wt. % of active carbon, the remainder being the matrixing materials, carbon black and PTFE.
Subsequent to the fibrillation step, the fibrillated material is dried, chopped and rolled at approx. 75° C. yielding the resulting coherent, self-sustaining and comparatively high tensile strength active layer sheet. Active carbon-containing active layer sheets produced in accordance with this invention characteristically have thicknesses of 0.010 to 0.025 inches (10 to 25 mils) with corresponding tensile strengths ranging from about 75 to 150 psi (measured after pressing in a hydraulic press at 81/2 T/in2 and 112° for three minutes).
The invention will be illustrated in further detail in the examples which follow in which all percents, ratios and parts are by weight unless otherwise indicated.
(A matrix active layer containing silver catalyzed active carbon particles.)
Commercially available ball milled "RB carbon" was found to have an ash content of approximately 12% as received. This "RB carbon" was treated in 38% KOH for 16 hours at 115° C. and found to contain 5.6% ash content after a subsequent furnace operation. The alkali treated "RB carbon" was then treated (immersed) for 16 hours at room temperature in 1:1 aqueous hydrochloric acid (20% concentration). The resulting ash content had been reduced to 2.8%. "RB carbon, deashed as above, was silvered in accordance with the following procedure:
Twenty (20 g) grams of deashed "RB carbon" were soaked in 500 ml of 0.161 N (normal) aqueous AgNO3 with stirring for two hours; the excess solution was filtered off to obtain a filter cake. The retrieved filtrate was 460 ml of 0.123 N AgNO3. The filter cake was rapidly stirred into an 85° C. alkaline formaldehyde solution, prepared using 300 cc (cubic centimeters) water, and 30 cc of 30% aqueous NaOH and 22 cc of 37% aqueous CH2 O, to ppt. Ag in the pores of the active carbon.
Calculation indicated that 79% of the 2.58 grams of retained silver in the catalyst was derived from adsorbed silver nitrate.
Separately, "Shawinigan Black," a commercially available acetylene carbon black, was teflonated with "Teflon 30" (duPont polytetrafluoroethylene dispersion), using an ultrasonic generator to obtain intimate mixture. 7.2 grams of the dried carbon black/PTFE mix was high speed chopped, spread in a dish, and then heat treated at 525° F. for 20 minutes. Upon removal and cooling, it was once again high speed chopped, this time for 10 seconds. Then 18 grams of the classified silvered active carbon was added to the 7.2 grams of carbon black-Teflon mix, high speed chopped for 15 seconds, and placed into a fiberizing (fibrillating) apparatus. The apparatus used for fiberizing consists of a Brabender Prep Center, Model D101, with an attached measuring head REO-6 on the Brabender Prep Center and medium shear blades were used. The mixture was added to the cavity of the mixer using 50 cc of a 30/70 (by volume) mixture of isopropyl alcohol in water as a lubricant to aid in fibrillating. The mixer was then run for 5 minutes at 30 rpm at 50° C., after which the material was removed as a fibrous coherent mass. This mass was then oven dried in a vacuum oven and was high speed chopped in preparation for rolling.
The chopped particulate material was then passed through a rolling mill, a Bolling rubber mill. The resulting matrix active layer sheet had an area density of 22.5 milligrams per square centimeter and was ready for lamination.
(A matrix active layer containing platinum catalyzed active carbon particles)
The procedure of Example 1 was repeated except that platinum was deposited on the deashed active ("RB") carbon instead of silver. The 10 to 20 micron classified deashed "RB" carbon had platinum applied thereto in accordance with the procedure described in U.S. Pat. No. 4,044,193 using H3 Pt(SO3)2 OH to deposit 1 wt. part platinum per 34 weight parts of deashed active carbon.
After fibrillation and upon rolling, the area density of the active layer was determined to be 22.2 milligrams per cm2. This matrix active layer was then ready for lamination.
(A matrix active layer containing silver catalyzed active carbon particles without heat treatment before fibrillation)
An active layer containing deashed, silvered "RB" active carbon was prepared as in Example 1 with the exception that the 70/30 (by weight) "Shawinigan Black/"Teflon 30" matrixing material was not heat treated before fabrillating. This matrix active layer was heavier than those prepared according to Examples 1 and 2. It had an area density of 26.6 milligrams per cm2 and was ready for lamination.
(A matrix active layer containing platinum catalyzed active carbon particles incorporating a pore former and heat treated, as in Examples 1 and 2, before fibrillation)
This matrix active layer was made according to the basic procedure of Example 1 using deashed "RB" active carbon platinized by the method of U.S. Pat. No. 4,044,193 to a level of 19 weight parts of deashed "RB" active carbon per weight part platinum. Six grams of ultrasonically teflonated (70:30, "Shawinigan Black":PTFE) carbon black were heat treated for 20 minutes at 525° F. prior to addition thereto of 15 grams of said active carbon along with 9 grams of sodium carbonate in isopropanol, which had been classified to the particle size range of +5 to -10 microns. This material was fibrillated and rolled out as in Example 1 and extracted by water (to remove the sodium carbonate) after first hot soaking it in ethylene glycol at 75° C. for 20 minutes.
The resulting active layer sheet was a very porous and light weight material.
(Forming laminated electrodes from the matrix active layers of Examples 1-3 and testing them in alkaline media at current densities of 250 milliamperes per square centimeter and higher.)
The active layers prepared in accordance with Examples 1 to 3, respectively, were each laminated to a current distributor and a backing sheet of sodium carbonate-loaded PTFE prepared as follows:
Two hundred cubic centimeters of isopropyl alcohol were poured into an "Osterizer" blender. Then 49 grams of duPont 6A polytetrafluoroethylene were placed in the blender and the PTFE--alcohol dispersionwas blended at the "blend" position for approximately one minute. The resulting slurry had a thick pasty consistency. Then another 100 cc of isopropyl alcohol were added in the blender and the mixture was blended (again at the "blend" position) for an additional two minutes.
Then 91 grams of particulate sodium carbonate in isopropanol (Ball milled and having an average particle size of approximately 3.5 microns, as determined by a Fisher Sub Sieve Sizer) were added to the blender. The PTFE--sodium carbonate mixture was then blended at the "blend" position in the "Osterizer" blender for three minutes followed by a higher speed blending at the "liquefying" position for an additional one minute. The resulting PTFE--sodium carbonate slurry was then poured from the blender on to a Buchner funnel and filtered and then placed in an oven at 80° C. where it was dried for three hours resulting in 136.2 grams yield of PTFE--sodium carbonate mixture. This mixture contained approximately 35 weight parts of PTFE and 65 weight parts of sodium carbonate.
This mixture was mildly fibrillated a Brabender Prep Center with attached Sigma mixer as described above.
After fibrillating, which compresses and greatly attenuates the PTFE, the fibrillated material is chopped to a fine dry powder using a coffee blender, i.e., Type Varco, Inc. Model 228.1.00 made in France. Chopping to the desired extent takes from about 5 to 10 seconds because the mix is friable. The extent of chopping can be varied as long as the material is finely chopped.
The chopped PTFE--Na2 CO3 mix is fed to six inch diameter chrome-plated steel rolls heated to about 80° C. Typically these rolls are set at a gap of 0.008 inch (8 mils) for this operation. The sheets are formed directly in one pass and are ready for use as backing layers in forming electrodes, e.g., oxygen cathodes, with no further processing beyond cutting, trimming to size and the like.
The current distributors had the below tabulated diameter and were nickel woven wire mesh having a 0.0003 inch thick silver plating and the woven strand arrangement tabulated below. The distributor was positioned on one active layer side while the backing layer was placed on the other side of the active layer.
The lamination was performed in a hydraulic press at 100° to 130° C. and using pressures of 4 to 8.5 tons per in2 for several minutes. These laminates were then hot soaked in ethylene glycol at 75° C. for 20 minutes before water washing at 65° C. for 18 hours. They were then dried.
The laminates were then placed in respective half cells for testing against a counter electrode in thirty percent aqueous sodium hydroxide at temperatures of 70° to 80° C. with an air flow of four times the theoretical requirement for an air cathode and at a current density of 300 milliamperes per cm2. The testing results and other pertinent notations are given below.
TABLE 1__________________________________________________________________________ActiveType of Ag Initial Voltage Useful LifeLayerPlated us. Hg/Hg/O Ref. of Matrix Voltage atExampleNi Mesh Electrode Electrode (hrs) Failure__________________________________________________________________________1 58 × 60 × .004 -0.265 volts 8,925 -.395 volts.sup.(1)2 50 × 50 × .005 -0.201 volts 3,512+ N.A..sup.(2)3 58 × 60 × .004 -0.282 volts 3,861 -.509 volts.sup.(3)__________________________________________________________________________ .sup.(1) Shortly after 8925 hours there was a steep decline in potential and the electrode was judged to haved failed. .sup.(2) After 188 days, its voltage was -0.246 volts compared to the Hg/HgO reference electrode (a very slight decline in potential) and this matrix electrode is still on life testing. After being started at 300 milliamperes per cm2, the test current density was changed to 250 milliamperes/cm2. .sup.(3) The final failure was caused by separation of the current distributor from the face of the electrode. It should be noted here tha in each of these "matrix" electrodes the approximate concentration of PTFE in the active layer mix is only about twelve (12) percent by weight. Prior to the "matrix" active layers of this invention, PTFE concentrations in active layers of approximately 20% were usually considered mandatory to obtain satisfactory electrodes. For example, prior to this invention PTFE concentrations in active layers of below about 18 wt. % yielded completely unsatisfactory electrodes. Hence it will be recognized that the "matrix" active layers of this invention enable considerably less Teflon to be used while still achieving the combined requirements of conductivity, strength, permeability and longevity long sought in air breathing electrodes.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3385780 *||Jul 10, 1964||May 28, 1968||Exxon Research Engineering Co||Porous dual structure electrode|
|US3409474 *||Jul 26, 1961||Nov 5, 1968||Varta Ag||Hydrogen storing electrode and process for its manufacture|
|US3462307 *||Apr 28, 1966||Aug 19, 1969||American Cyanamid Co||Metal-air battery including fibrillated cathode|
|US3838064 *||Sep 19, 1972||Sep 24, 1974||Kewanee Oil Co||Process for dust control|
|US3838092 *||Dec 20, 1972||Sep 24, 1974||Kewanee Oil Co||Dustless compositions containing fiberous polytetrafluoroethylene|
|US3935029 *||Feb 19, 1974||Jan 27, 1976||Energy Research Corporation||Method of fabricating a carbon - polytetrafluoroethylene electrode - support|
|US4058482 *||Dec 20, 1976||Nov 15, 1977||United Technologies Corporation||Fuel cell electrode|
|US4150076 *||May 23, 1977||Apr 17, 1979||United Technologies Corporation||Fuel cell electrode and method of manufacture of sheet material for use therein|
|US4170540 *||Mar 31, 1978||Oct 9, 1979||Hooker Chemicals & Plastics Corp.||Method for forming microporous membrane materials|
|1||*||Iliev, I., Journal of Power Sources, "On the Effect on Various Active Carbon Catalysts on the Behavior of Carbon Gas Diffusion Air Electrodes: 1. Alkaline Solutions," vol. 1, pp. 35-46, 1976/1977.|
|2||*||Landi, H. P., et al., "Advances in Chemistry Series," American Chemical Society Publications, pp. 13-23, 1969.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4447505 *||Dec 1, 1981||May 8, 1984||Electrochemische Energieconversie, N.V.||Fuel cell electrode|
|US4500647 *||Sep 28, 1982||Feb 19, 1985||Diamond Shamrock Chemicals Company||Three layer laminated matrix electrode|
|US4518705 *||Sep 28, 1982||May 21, 1985||Eltech Systems Corporation||Three layer laminate|
|US4551220 *||Jul 28, 1983||Nov 5, 1985||Asahi Glass Company, Ltd.||Gas diffusion electrode material|
|US4631200 *||May 17, 1985||Dec 23, 1986||The Dow Chemical Company||Graphite composite chips|
|US4647359 *||Oct 16, 1985||Mar 3, 1987||Prototech Company||Electrocatalytic gas diffusion electrode employing thin carbon cloth layer|
|US4693946 *||Mar 11, 1986||Sep 15, 1987||Eltech Systems Corporation||Battery with modular air cathode and anode cage|
|US4719156 *||Mar 5, 1987||Jan 12, 1988||Eltech Systems Corporation||Efficient electrical power generation system|
|US4722773 *||Oct 17, 1984||Feb 2, 1988||The Dow Chemical Company||Electrochemical cell having gas pressurized contact between laminar, gas diffusion electrode and current collector|
|US4756980 *||Jun 22, 1987||Jul 12, 1988||Eltech Systems Corporation||Battery with modular air cathode and anode cage|
|US4788111 *||Aug 24, 1987||Nov 29, 1988||Eltech Systems Corporation||Efficient electrical power generation system|
|US4788764 *||Jan 26, 1988||Dec 6, 1988||Eltech Systems Corporation||Method of making a unitized electrode assembly|
|US4828939 *||Jun 1, 1987||May 9, 1989||Eltech Systems Corporation||Bipolar metal/air battery|
|US4927717 *||Apr 3, 1989||May 22, 1990||Eltech Systems Corporation||Bipolar metal/air battery|
|US5009971 *||Aug 9, 1989||Apr 23, 1991||Ppg Industries, Inc.||Gas recombinant separator|
|US5306579 *||Oct 30, 1992||Apr 26, 1994||Aer Energy Resources, Inc.||Bifunctional metal-air electrode|
|US5639568 *||Oct 16, 1995||Jun 17, 1997||Aer Energy Resources, Inc.||Split anode for a dual air electrode cell|
|US6127474 *||Aug 27, 1997||Oct 3, 2000||Andelman; Marc D.||Strengthened conductive polymer stabilized electrode composition and method of preparing|
|US6479188||Oct 13, 1999||Nov 12, 2002||The Gillette Company||Cathode tube and method of making the same|
|US6627252||May 12, 2000||Sep 30, 2003||Maxwell Electronic Components, Inc.||Electrochemical double layer capacitor having carbon powder electrodes|
|US6643119||Nov 2, 2001||Nov 4, 2003||Maxwell Technologies, Inc.||Electrochemical double layer capacitor having carbon powder electrodes|
|US6673533 *||Sep 17, 1997||Jan 6, 2004||Meso Scale Technologies, Llc.||Multi-array multi-specific electrochemiluminescence testing|
|US6794074||Oct 12, 2001||Sep 21, 2004||Rayovac Corporation||Air manager for metal-air cells|
|US6946007||Sep 12, 2003||Sep 20, 2005||Sony Corporation||Electrochemical double layer capacitor having carbon powder electrodes|
|US6955694||Jan 30, 2003||Oct 18, 2005||Maxwell Technologies, Inc.||Electrochemical double layer capacitor having carbon powder electrodes|
|US7005213||May 16, 2002||Feb 28, 2006||Rayovac Corporation||Ionically conductive additive for zinc-based anode in alkaline electrochemical cells|
|US7227737||Oct 27, 2004||Jun 5, 2007||Maxwell Technologies, Inc.||Electrode design|
|US7245478||Jul 8, 2005||Jul 17, 2007||Maxwell Technologies, Inc.||Enhanced breakdown voltage electrode|
|US7295423||Apr 2, 2004||Nov 13, 2007||Maxwell Technologies, Inc.||Dry particle based adhesive electrode and methods of making same|
|US7318374||Jan 21, 2004||Jan 15, 2008||Victor Guerrero||Wire cloth coffee filtering systems|
|US7332238||Sep 6, 2002||Feb 19, 2008||The Gillette Company||Electrochemical cells and systems|
|US7342770||Apr 2, 2004||Mar 11, 2008||Maxwell Technologies, Inc.||Recyclable dry particle based adhesive electrode and methods of making same|
|US7352558||Apr 2, 2004||Apr 1, 2008||Maxwell Technologies, Inc.||Dry particle based capacitor and methods of making same|
|US7382046||Mar 16, 2004||Jun 3, 2008||Fujitsu Limited||Semiconductor device protection cover, and semiconductor device unit including the cover|
|US7461587||Sep 7, 2006||Dec 9, 2008||Victor Guerrero||Beverage container with wire cloth filter|
|US7492571||Oct 14, 2005||Feb 17, 2009||Linda Zhong||Particles based electrodes and methods of making same|
|US7492574||Dec 8, 2005||Feb 17, 2009||Maxwell Technologies, Inc.||Coupling of cell to housing|
|US7495349||Jul 28, 2004||Feb 24, 2009||Maxwell Technologies, Inc.||Self aligning electrode|
|US7508651||Apr 2, 2004||Mar 24, 2009||Maxwell Technologies, Inc.||Dry particle based adhesive and dry film and methods of making same|
|US7563537||Nov 30, 2005||Jul 21, 2009||Rovcal, Inc.||Ionically conductive clay additive for use in electrochemical cells|
|US7722686||Jul 17, 2006||May 25, 2010||Maxwell Technologies, Inc.||Composite electrode and method for fabricating same|
|US7791860||Apr 2, 2004||Sep 7, 2010||Maxwell Technologies, Inc.||Particle based electrodes and methods of making same|
|US7791861||Jan 31, 2008||Sep 7, 2010||Maxwell Technologies, Inc.||Dry particle based energy storage device product|
|US7811337||Feb 27, 2008||Oct 12, 2010||Maxwell Technologies, Inc.||Ultracapacitor electrode with controlled sulfur content|
|US7851238||Feb 24, 2009||Dec 14, 2010||Maxwell Technologies, Inc.||Method for fabricating self-aligning electrode|
|US7858321||Sep 10, 2002||Dec 28, 2010||Meso Scale Technologies, Llc||Methods and apparatus for conducting multiple measurements on a sample|
|US7859826||Mar 6, 2008||Dec 28, 2010||Maxwell Technologies, Inc.||Thermal interconnects for coupling energy storage devices|
|US7883553||Jun 10, 2008||Feb 8, 2011||Maxwell Technologies, Inc.||Method of manufacturing an electrode product|
|US7920371||Aug 2, 2009||Apr 5, 2011||Maxwell Technologies, Inc.||Electrical energy storage devices with separator between electrodes and methods for fabricating the devices|
|US7935155||May 16, 2008||May 3, 2011||Maxwell Technologies, Inc.||Method of manufacturing an electrode or capacitor product|
|US8072734||Jan 31, 2008||Dec 6, 2011||Maxwell Technologies, Inc.||Dry particle based energy storage device product|
|US8164181||Aug 31, 2010||Apr 24, 2012||Fujitsu Semiconductor Limited||Semiconductor device packaging structure|
|US8213156||Nov 17, 2009||Jul 3, 2012||Maxwell Technologies, Inc.||Particle based electrodes and methods of making same|
|US8268670||Sep 22, 2011||Sep 18, 2012||Fujitsu Semiconductor Limited||Method of semiconductor device protection|
|US8518573||Dec 24, 2009||Aug 27, 2013||Maxwell Technologies, Inc.||Low-inductive impedance, thermally decoupled, radii-modulated electrode core|
|US8722323||Nov 2, 2010||May 13, 2014||Meso Scale Technologies Llp||Multi-array, multi-specific electrochemiluminescence testing|
|US8815443||Mar 10, 2010||Aug 26, 2014||Maxwell Technologies, Inc.||Dry-particle based adhesive and dry film and methods of making same|
|US9354230||Dec 23, 2010||May 31, 2016||Meso Scale Technologies, Llc.||Methods and apparatus for conducting multiple measurements on a sample|
|US9525168||Aug 22, 2014||Dec 20, 2016||Maxwell Technologies, Inc.||Dry-particle based adhesive and dry film and methods of making same|
|US20020061427 *||Oct 12, 2001||May 23, 2002||Vu Viet H.||Air manager for metal-air cells|
|US20020093783 *||Nov 1, 2001||Jul 18, 2002||Priya Bendale||Electrochemical double layer capacitor having carbon powder electrodes|
|US20020177043 *||May 16, 2002||Nov 28, 2002||Ernest Ndzebet||Ionically conductive additive for zinc-based anode in alkaline electrochemical cells|
|US20030086238 *||Nov 2, 2001||May 8, 2003||Maxwell Technologies, Inc., A Delaware Corporation||Electrochemical double layer capacitor having carbon powder electrodes|
|US20030113713 *||Sep 10, 2002||Jun 19, 2003||Meso Scale Technologies, Llc||Methods and apparatus for conducting multiple measurements on a sample|
|US20040048121 *||Sep 6, 2002||Mar 11, 2004||Sathya Motupally||Electrochemical cells and systems|
|US20040048146 *||Sep 6, 2002||Mar 11, 2004||David Adamson||Electrochemical cells and systems|
|US20050250011 *||Apr 27, 2005||Nov 10, 2005||Maxwell Technologies, Inc.||Particle packaging systems and methods|
|US20050266298 *||Apr 2, 2004||Dec 1, 2005||Maxwell Technologies, Inc.||Dry particle based electro-chemical device and methods of making same|
|US20050271798 *||Jul 6, 2005||Dec 8, 2005||Maxwell Technologies, Inc.||Electrode formation by lamination of particles onto a current collector|
|US20060114643 *||Oct 14, 2005||Jun 1, 2006||Maxwell Technologies, Inc.||Particles based electrodes and methods of making same|
|US20060133012 *||Apr 2, 2004||Jun 22, 2006||Maxwell Technologies, Inc.||Dry particle based capacitor and methods of making same|
|US20060133013 *||Apr 2, 2004||Jun 22, 2006||Maxwell Technologies, Inc.||Dry particle based adhesive and dry film and methods of making same|
|US20060137158 *||Oct 14, 2005||Jun 29, 2006||Maxwell Technologies, Inc.||Dry-particle packaging systems and methods of making same|
|US20060146475 *||Apr 2, 2004||Jul 6, 2006||Maxwell Technologies, Inc||Particle based electrodes and methods of making same|
|US20060146479 *||Apr 2, 2004||Jul 6, 2006||Maxwell Technologies, Inc.||Recyclable dry particle based adhesive electrode and methods of making same|
|US20060246343 *||Oct 14, 2005||Nov 2, 2006||Maxwell Technologies, Inc.||Dry particle packaging systems and methods of making same|
|US20070008678 *||Dec 8, 2005||Jan 11, 2007||Maxwell Technologies, Inc.||Coupling of cell to housing|
|US20070026317 *||Jul 17, 2006||Feb 1, 2007||Porter Mitchell||Composite electrode and method for fabricating same|
|US20070048575 *||Aug 30, 2005||Mar 1, 2007||Rovcal, Inc.||Electrochemical cells containing spun mercury-amalgamated zinc particles having improved physical characteristics|
|US20070048576 *||Jun 1, 2006||Mar 1, 2007||Rovcal, Inc.||Electrochemical cells containing spun mercury-amalgamated zinc particles having improved physical characteristics|
|US20070122698 *||Oct 14, 2005||May 31, 2007||Maxwell Technologies, Inc.||Dry-particle based adhesive and dry film and methods of making same|
|US20070122709 *||Nov 30, 2005||May 31, 2007||Rovcal, Inc.||Ionically conductive clay additive for use in electrochemical cells|
|US20070198230 *||Feb 20, 2006||Aug 23, 2007||Ford Global Technologies, Llc||Parametric modeling method and system for conceptual vehicle design|
|US20080016664 *||May 22, 2007||Jan 24, 2008||Maxwell Technologies, Inc.||Electrode design|
|US20080092808 *||Oct 24, 2007||Apr 24, 2008||Maxwell Technologies, Inc.||Dry Particle Based Adhesive Electrode and Methods of Making Same|
|US20080102371 *||Nov 13, 2007||May 1, 2008||Maxwell Technologies, Inc.||Dry particle based adhesive electrode and methods of making same|
|US20080117564 *||Jan 31, 2008||May 22, 2008||Maxwell Technologies, Inc.||Dry particle based energy storage device product|
|US20080117565 *||Jan 31, 2008||May 22, 2008||Maxwell Technologies, Inc.||Dry particle based energy storage device product|
|US20080201925 *||Feb 28, 2007||Aug 28, 2008||Maxwell Technologies, Inc.||Ultracapacitor electrode with controlled sulfur content|
|US20080266752 *||Mar 6, 2008||Oct 30, 2008||Maxwell Technologies, Inc.||Thermal interconnects for coupling energy storage devices|
|US20090029196 *||Jul 27, 2007||Jan 29, 2009||More Energy Ltd.||Dry method of making a gas diffusion electrode|
|US20090223630 *||Feb 24, 2009||Sep 10, 2009||Maxwell Technologies, Inc.||Method for Self Aligning Electrode|
|US20090290288 *||Aug 2, 2009||Nov 26, 2009||Maxwell Technologies, Inc.||Electrical energy storage devices with separator between electrodes and methods for fabricating the devices|
|US20100014215 *||Oct 14, 2005||Jan 21, 2010||Maxwell Technologies, Inc.||Recyclable dry particle based electrode and methods of making same|
|US20100033901 *||Aug 2, 2009||Feb 11, 2010||Maxwell Technologies, Inc.||Dry-particle based adhesive electrode and methods of making same|
|US20100097741 *||Feb 27, 2008||Apr 22, 2010||Maxwell Technologies, Inc.||Ultracapacitor electrode with controlled sulfur content|
|US20100110613 *||Feb 27, 2008||May 6, 2010||Maxwell Technologies, Inc.||Ultracapacitor electrode with controlled iron content|
|US20110049699 *||Aug 31, 2010||Mar 3, 2011||Fujitsu Semiconductor Limited||Method of semiconductor device protection, package of semiconductor device|
|US20110105354 *||Dec 23, 2010||May 5, 2011||Meso Scale Technologies, Llc||Methods and Apparatus for Conducting Multiple Measurements on a Sample|
|US20110114896 *||Jun 16, 2010||May 19, 2011||Maxwell Technologies, Inc.,||Dry-particle packaging systems and methods of making same|
|US20110165318 *||Jul 6, 2005||Jul 7, 2011||Maxwell Technologies, Inc.||Electrode formation by lamination of particles onto a current collector|
|CN102002724A *||Apr 23, 2010||Apr 6, 2011||王伟||Acetylene black cathode provided with waterproof membrane and used for producing hydrogen peroxide and manufacturing method thereof|
|CN102002724B||Apr 23, 2010||Aug 17, 2011||王伟||Acetylene black cathode provided with waterproof membrane and used for producing hydrogen peroxide and manufacturing method thereof|
|EP0763836A3 *||Aug 9, 1996||Apr 14, 1999||Nisshinbo Industries, Inc.||Polarizable electrode for electric double-layer capacitor, and electric double-layer capacitor using said polarizable electrode|
|WO2009016521A2 *||Jul 23, 2008||Feb 5, 2009||More Energy Ltd.||Dry method of making a gas diffusion electrode|
|WO2009016521A3 *||Jul 23, 2008||Dec 30, 2009||More Energy Ltd.||Dry method of making a gas diffusion electrode|
|WO2012129532A1||Mar 23, 2012||Sep 27, 2012||Andelman Marc D||Polarized electrode for flow-through capacitive deionization|
|U.S. Classification||502/101, 204/294, 502/159, 429/535, 429/524, 429/530|
|International Classification||C25B11/12, C25B11/06, C25B11/03, C25B11/04, C25B11/00, C25B1/46, C25B11/02|
|Feb 1, 1983||CC||Certificate of correction|
|Nov 7, 1983||AS||Assignment|
Owner name: DIAMOND SHAMROCK CHEMICALS COMPANY
Free format text: CHANGE OF NAME;ASSIGNOR:DIAMOND SHAMROCK CORPORATION CHANGED TO DIAMOND CHEMICALS COMPANY;REEL/FRAME:004197/0130
|Apr 12, 1985||AS||Assignment|
Owner name: ELTECH SYSTEMS CORPORATION 6100 GLADES ROAD, BOCA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:DIAMOND SHAMROCK CHEMICALS COMPANY;REEL/FRAME:004388/0130
Effective date: 19850410